Nozzle structure and arrangement for producing high octane alkylate

ABSTRACT

A nozzle having several outlet orifices, including a centrally disposed orifice and at least one additional or subordinate orifice disposed adjacent to the first-mentioned orifice, is provided so that in an alkylation of an isoparaffin with an olefin the recycle isoparaffin which contains catalyst therein, usually hydrogen fluoride catalyst, can be brought into contact with hydrogen fluoride-free olefin feed at the moment when this feed encounters the main body of catalyst. Conduits are provided to supply recycle isoparaffin usually to the adjacent or subordinate nozzle, and make up isoparaffin and the olefin feed to the central or axial orifice.

United States Patent MAKE- UP ISOPARAFFIN FRESH 13 OLEFIN\ 15] 3,696,168 Vanderveen [451 Oct. 3, 1972 NOZZLE STRUCTURE AND 2,701,184 2/1955 Rupp ..260/683.59 ARRANGEMENT FOR PRODUCING 2,430,333 11/1947 Hadden ..260/683.52 HIGH OCTANE ALKYLATE Pn'mary Examiner-Delbert E. Gantz 72 1 t nven or gilt]: W Vanderveen, Bartlesville, Assistant Examiner G J Crasanakis Attorney-Young and Quigg [73] Assignee: Philips Petroleum Company 22 Filed: Sept. 21, 1970 [57] ABSTRACT [21] Appl No; 73,790 A nozzle having several outlet orifices, including a centrally dlsposed orifice and at least one additional or subordinate orifice disposed adjacent to the first- U-S- mentioned orifice is provided so in an alkylation Cl- .i i ..C07C f a an olefin recycle isoparaffin [58] Field of Search.....260/683.58, 683.59, 683.4 R, which contains catalyst therein usually hydrogen 260/683.43, 683.48, 683.52, 683.53; 23 fluoride catalyst, can be brought into contact with h dro en fluoride-free olefin feed at the moment [56] References C'ted w hen this feed encounters the main body of catalyst. UNITED STATES PATENTS Conduits are provided to supply recycle isoparaffin usually to the adjacent or subordinate nozzle, and 1,536,463 5/1925 Westhng ..23/285 make up i ffi and the l fi f d to the central 3,285,712 11/ 1966 Matasa et a1. ..23/285 or axial orifice 2,751,425 6/1956 Rupp ..260/683.59 3,082,274 3/1963 Mayer ..260/683.58 6Claims,4Drawing Figures HYDROCARBON T0 FURTHER PROCESSING HYDROCARBON PHASE .3 COOLANT CATALYST PHASE (L 10 RECYLE 1SOPARAFF 1N 15c lsd CONTAINING CATALYSTJ is PATENTEDUDT 3 1972 sum 1 or z INVENTOR. J. W. VANDERVEEN A 7' TORNEYS NOZZLE STRUCTURE AND ARRANGEMENT FOR PRODUCING I-IIGI-I OCTANE ALKYLATE This invention relates to a nozzle for the production of high octane alkylate. It also relates to a process for the production of high octane alkylate by the alkylation of an isoparaffin with an olefin in the presence of a catalyst. Further, it relates to the alkylation of an isoparaffin with an olefin in the presence of hydrogen fluoride catalyst.

According to a concept of the invention, there is provided a nozzle structure in which there are several orifices, each orifice being provided with a supply conduit, the orifices being arranged in a compound fashion to permit discharge from them all simultaneously to the main body of catalyst oracid. In a further concept of the invention, it provides an alkylation nozzle arrangement in which one or more nozzle assemblies as herein described are positioned within an alkylation reactor. In a still further concept of the invention, it provides a process for the alkylation of an isoparaffin with an olefin in the presence of a catalyst, for example, hydrogen fluoride catalyst, wherein recycle isoparafiin is discharged though at least one nozzle peripheral to another nozzle through which catalyst or acid-free isoparaffin and catalyst or acid-free olefin feed are ejected into the main catalyst body.

Presently, there is being made a very great effort to produce increased amounts of high octane, lead-free or substantially lead-free gasolines. It has been known to produce isoparaffin-olefin alkylate for use as a blending stock in the production of high quality gasolines.

It has been noted in experiments which have been performed that in a plant operation in which I-IF alkylation is being performed the alkylation reaction is completed within about 1 foot distance of the riser and that a relatively low octane alkylate is producedbecause of poor cooling by the acid in the reactor. Thus, a reaction at the lowest possible temperature will give the highest octane of the alkylate. Also, it appears desirable to defer anyalkylation of olefin with the isoparaffin until all of the reactants are in presence of a substantial body of the catalyst.

It is known that recycle isoparaffin, e.g., recycle isobutane, is ordinarily saturated with the acid catalyst, e.g., hydrogen fluoride. It is also known to be essential to have the isoparaffin to olefin ratio as high as possible to avoid undesirable side reactions.-

l have conceived a compound nozzle for transferring into the main body of the catalyst or acid in the reactor not only the recycle isoparaffin which contains some catalyst but also the feeds of isoparaffin and olefin which are acid free so that all of the reactants and all of the acid will be intermingled rapidly with least possible rise in temperature. The compound nozzle uses momentum transfer to induct reactor acid into the nozzle as a cooling medium to be there present even as alkylation is initiated. This cooling medium will transfer away the heat of reaction when the recycle isoparaffin droplets collide with the olefin droplets. Some reaction will occur when the acid penetrates the pure olefinisobutane which is in a mol ratio of approximately 121, usually. However, the contact time in the nozzle of the invention is of the order of milliseconds compared with an acid penetration time of the order of 1-2 seconds, or

more.

To further subdivide the mixing time and to increase the fullest possible contact under any particular set of operating conditions, the concept which contemplates the use of a plurality of nozzles to permit maintaining a lower temperature or less local heat buildup within any particular nozzle is now one of the preferred embodiments of the invention. Thus, a hot spot which is highly localized can be subdivided. Thus, by surrounding at least a portion of the reactor with a plurality of such nozzles, the size of each and therefore the temperature or heat buildup in each is further reduced with respect to the precise points of intimate contact of the acid initially with the isobutane-olefin mix.

It is an object of this invention to provide an improved injection means for conducting an isoparaffinolefin alkylation. It is another object of the invention to provide an improved contacting of an isoparaffin-olefin mixture with an alkylation catalyst. A still further object of the invention is to provide a process for the alkylation of an isoparaffin-olefin in the presence of an acid catalyst, e.g., hydrofluoric acid. Still another object of the invention is to provide a means for avoiding contact of recycle isoparaffin stream, containing acid catalyst, with olefin until such time as all are within the main reaction mass. Further still, it is an object of the invention, in an acid isoparaffin-olefin alkylation, to reduce the temperature at the initial contacting of the isoparaffin-olefin mixture with the main reaction mass.

Other aspects, concepts, objects and several advantages of the invention are apparent from a study of this disclosure, drawing and appended claims.

According to the present invention, there is provided at least one nozzle for injecting into a reaction mass,

I comprising isoparaffin, olefin and acid catalyst, fresh isoparaffin, e.g., isobutane, which is catalyst-free, fresh olefin, which is catalyst or acid free, and a recycle isoparaffin, which contains some acid catalyst therein, the structure providing adjacently disposed nozzles for ejecting their respective fluids into the reaction mass and conduits in communication with said nozzles whereby to separately but intimately admix into the reaction mass, virtually simultaneously, the recycle isoparaffin, the nonacid containing fresh feed of isoparaffin and olefin, and the catalyst.

Still according to the invention, there is provided adjacent such a compound nozzle system or structure as herein described, axially disposed with respect thereto, and induction means, for example, a hood open at its peak to permit fluid ejected from the nozzles to draw into the base of the hood, rapidly from the mass of catalyst in a reactor in which the said structure is placed the catalyst for rapid intimate admixture simultaneously with the fresh feed and with the recycle isoparaffin stream.

In the drawing in FIG. 1, there is shown a structure in diagrammatic form of a nozzle according to the invention.

In FIG. 1a is shown a horizontal cross section of FIG. 1 along the line 1a1a.

In FIG. 2 is shown a reactor, also in diagrammatic form, having disposed therein a plurality of nozzles according to FIG. 1. The nozzles in FIG. 2 are shown in simplified form. That is, their details are omitted.

In FIG. 3 is shown, also in diagrammatic form, an HP alkylation system having a riser-reactor, and having disposed therein a plurality of the nozzles of my invention.

Referring now to FIG. 1, there are provided a central or axially disposed feed nozzle 2 surrounded by subordinate or auxiliary nozzles 3. Makeup isobutane free of 5 catalyst enters 4. Olefin feed free of catalyst enters at 5 and the mixing of fresh isobutane and olefin is accomplished during the course of travel in section 6 of nozzle 2, and there is formed an isobutane-olefin feed, usually containing C and C and sometimes C olefins, as is known in the art. A single entry 4 or 5 can be used for admixed makeup isobutane and olefin feed. Recycle isobutane enters the nozzle system through at least one inlet 7, is distributed through header 8, and is ejected from at least one nozzle 3 in the immediate proximity of the fluid emanating from nozzle 2. The ejecting force or momentum of the fluids leaving nozzles 2 and 3 draws in or inducts reactor acid or catalyst as shown by the arrow at 9 through passageway 11 into the mixing chamber of the overall nozzle system formed by conically shaped, cap or mantle l0. Passage 11 is formed by the conical portions of 10 and 11' on skirt 10'.

FIG. 1a shows nozzle skirt 10', manifold 8, nozzles 3 (four are illustrated) and axial zone 6 of nozzle 2.

Referring now to FIG. 2, it will be seen there are three main piping connections to each of four separately disposed nozzles which can be in any desired arrangement within the fluid filled reactor 12. More or less than four nozzles can be used. Thus, isoparafiin feed, that is, isoparaffin containing no acid or HF catalyst therein is passed by line 13 and associated lines 13a, 13b, 13c and 13d into the respective nozzle structures disposed in the reactor. Similarly, fresh olefin feed enters through 14 and associated pipes 14a, 14b, 14c and 14d and into the nozzles. Finally, recycle isoparaffin containing acid enters by pipe 15 and associated delivery pipes 15a, 15b, 15c, and 15d and into the nozzles as already described in connection with FIG. 1.

Referring now to FIG. 3, there is provided an HF alkylation operation using a modern riser-reactor, for example as described in U.S. Pat. No. 3,213,157 issued Oct. 19, 1965, to Hays et al. and US. Pat. No. 3,281,213 issued Oct. 25, 1966, to Waddill. Numeral 100 is a riser-reactor from which hydrocarbon-catalyst liquid emulsion is continuously removed and charged to phase separator 101. Liquid hydrocarbon is removed from separator 101 and passed via conduit 102 to a fractionation zone 103 from which are recovered propane 104, normal butane 105, total alkylate 106, and recycle isobutane containing HF catalyst in solution. Also from separator 101 there is recovered via 108 the HF acid catalyst phase which is cooled 109 and returned to reactor 100 via conduit 110. Fresh isobutane and fresh olefins are admixed and charged via conduit 111 through branch conduits 112, 113 and 114 to nozzle assemblies 116, 117 and 118, exiting via outlets 2 thereof as shown in FIG. 1. Recycle isobutane, saturated with HF catalyst, is charged to the auxiliary nozzles 3 of the nozzle assemblies via conduit 107 and branch conduits 119, 120 and 121. (Three nozzle assemblies are shown in FIG. 3 for illustrative purposes only. More than three nozzle assemblies will be used in plant operations ordinarily.) The nozzles preferably terminate at different levels throughout the cross section of the reactor 100 for optimum operation.

It will be seen upon a study of the disclosure and the drawing that various arrangements are possible to obtain within the reactors l2 and whatever overall flow and local flows as desired to control the temperature in the overall reactor and in each nozzle location. The nozzles can be so arranged as to complement the momentum of each with that of the other or the momentums can be substantially equal and opposite or some can be in onedirection and others in another.

The following is an example giving the reaction conditions which are generally known for the alkylation of isobutane with a mixture of olefins. The temperature and reaction time are noted. The octane number is compared with similar reaction conditions for an alkylation as presently conducted in the art. It will be seen that there have been obtained a very worthwhile increase in octane number with corresponding reduction of overall temperature as well as the temperature in the immediate or exact points of contact of the reactants and catalyst.

EXAMPLE A liquid-liquid HF catalytic alkylation of isobutane with mixed butylenes to produce high octane motor fuel, at about 90F. and a pressure to maintain liquid phase is now compared with operation using my invention. The systems compared herein are the riser-reactor operations of FIG. 3. The conventional operation uses conventional nozzles (see US. Pat. No. 3,213,157). The nozzles of both operations are used in the same number and located in the same manner within the reactor-riser so comparison is readily made. The recycle isobutane in both runs contains about 0.52 weight percent HF in solution. The fresh isobutane and fresh olefin are HF-free. The HF acid to total hydrocarbon liquid volume ratio, the recycle isobutane to olefin mol ratio, and the fresh isobutane to olefin mol ratio in the conventional run and in the run of the invention are, respectively, 7:1, 10:1, and 1.111.

Motor fuel produced by the conventional run and the invention run are, respectively, 93.0 and 94.5 Research Octane with no tetraethyl lead.

The reactor in this comparison contains about cubic feet of reaction mass. The rate at which total isoparaffin and olefin enter the reactor is about 10,000 barrels/day. The acid, including makeup and/or regenerated acid is cycled at a rate of about 70,000 barrels/day.

It will be understood that while the nozzles have been shown and described to be juxtapositioned with their axes parallel, it is within the scope of the invention to juxtaposition them otherwise, even to discharge with opposite momenta. However, where inducting of the acid is desired it will be necessary, when the momentum of the injected fluids is to be employed for this purpose, to so arrange the acid entry that one or more ejected streams of the streams passing from the nozzles will accomplish the desired result. The relative ejection velocities and consequent momenta, as well as any angle of one nozzle respecting another will be considered. Thus, one or more auxiliary nozzles can be oriented to discharge at an angle, at say 45, 90or l20into the main stream, or vice versa.

Reasonable variation and modification are possible within the scope of the foregoing disclosure, the drawing and the appended claims to the invention the essence of which is that there have been provided a novel structural nozzle arrangement and use thereof in an alkylation operation in which isoparaffin is alkylated with an olefin in the presence of a catalyst contact of which with the olefin is undesired until all of the olefin and isoparaffin in desired ratios have been brought into intimate contact each with the other and with the catalyst; the structure of the nozzle means of the invention providing separate but juxtapositioned nozzles for the recycle of isoparaffin stream containing acid and for the acid or catalyst free isoparaffin and olefin fed to the operation, substantially as described.

I claim: 7

l. A nozzle structure suitable for the alkylation of an isoparaffin with an olefin in the presence of an acid catalyst which comprises a nozzle mantel, a nozzle skirt, said skirt being placed at one end of said mantel, said mantel having at the other end thereof a discharge opening substantially smaller than its largest diameter, said mantel and said skirt being axially aligned and spaced to provide a peripheral opening between said skirt and at the largest diameter of said mantel, at least two injector nozzles in close proximity each to the other having their discharge ends encompassed within said skirt and mantle at about said peripheral opening, said injector nozzles being axially aligned and having their discharge ends oriented into said mantel and means for delivering to said injector nozzles respectively recycle isoparaffin and fresh isoparaffin and olefin feed, the nozzle structure thus defined being disposed within an alkylation reactor.

2. A structure as described in claim 1 wherein there is a central feed nozzle as for feeding fresh isoparaffin and fresh olefin into the system and there are provided surrounding said nozzle a plurality of discharge nozzles for feeding into the discharge of said central nozzle recycle isoparaffin containing acid whereby to provide for intimate intermingling of all of the herein mentioned streams with acid inducted from said reactor into said peripheral opening between said mantel and said skirt.

3. A process for the alkylation of isoparaffin with an olefin in the presence of an acid catalyst wherein the isoparaffin, the olefin, and recycle isoparaffin are injected into an isoparaffin-olefin acid catalyzed reaction zone located in an alkylation reactor according to claim 1.

4. A process for the alkylation of isoparaffin with an olefin in the presence of an acid catalyst wherein the isoparaffin, the olefin, and recycle isoparaffin are injected into an isoparaffin-olefin acid catalyzed reaction zone employing at least one structure according to claim 2.

5. A plurality of nozzle structures suitable for the alkylation of an isoparaffin with an olefin in the presence of an acid catalyst, each of said structures comprising a nozzle mantel, a nozzle skirt, said skirt being placed at one end of said mantel, said mantel having at the other end thereof a discharge opening substantially smaller than its largest diameter, said mantel and said skirt being axially aligned and spaced to provide a peripheral opening between said skirt and at the largest diameter of said mantel, at least two injector nozzles in close proximity each to the other having their discharge ends encompassed within said skirt and mantle at about said peripheral opening, said in ector nozzles being axially aligned and having their discharge ends oriented into said mantel and means for delivering to said injector nozzles respectively recycle isoparaffin and fresh isoparaffin and olefin feed, the nozzles structures thus defined being disposed within an alkylation reactor.

6. A process for the alkylation of isoparaffin with an olefin in the presence of an acid catalyst wherein the isoparaffin, the olefin, and recycle isoparaffin are injected into an isoparaffin-olefin acid catalyzed reaction 

2. A structure as described in claim 1 wherein there is a central feed nozzle as for feeding fresh isoparaffin and fresh olefin into the system and there are provided surrounding said nozzle a plurality of discharge nozzles for feeding into the discharge of said central nozzle recycle isoparaffin containing acid whereby to provide for intimate intermingling of all of the herein mentioned streams with acid inducted from said reactor into said peripheral opening between said mantel and said skirt.
 3. A process for the alkylation of isoparaffin with an olefin in the presence of an acid catalyst wherein the isoparaffin, the olefin, and recycle isoparaffin are injected into an isoparaffin-olefin acid catalyzed reaction zone located in an alkylation reactor according to claim
 1. 4. A process for the alkylation of isoparaffin with an olefin in the presence of an acid catalyst wherein the isoparaffin, the olefin, and recycle isoparaffin are injected into an isoparaffin-olefin acid catalyzed reaction zone employing at least one structure according to claim
 2. 5. A plurality of nozzle structures suitable for the alkylation of an isoparaffin with an olefin in the presence of an acid catalyst, each of said structures comprising a nozzle mantel, a nozzle skirt, said skirt being placed at one end of said mantel, said mantel having at the other end thereof a discharge opening substantially smaller than its largest diameter, said mantel and said skirt being axially aligned and spaced to provide a peripheral opening between said skirt and at the largest diameter of said mantel, at least two injector nozzles in close proximity each to the other having their discharge ends encompassed within said skirt and mantle at about said peripheral opening, said injector nozzles being axially aligned and having their discharge ends oriented into said mantel and means for delivering to said injector nozzles respectively recycle isoparaffin and fresh isoparaffin and olefin feed, the nozzles structures thus defined being disposed within an alkylation reactor.
 6. A process for the alkylation of isoparaffin with an olefin in the presence of an acid catalyst wherein the isoparaffin, the olefin, and recycle isoparaffin are injected into an isoparaffin-olefin acid catalyzed reaction zone located in an alkylation reactor according to claim
 5. 